CN110153442B - Nano gold-silver alloy solution with affinity to fibers and preparation method thereof - Google Patents
Nano gold-silver alloy solution with affinity to fibers and preparation method thereof Download PDFInfo
- Publication number
- CN110153442B CN110153442B CN201910518947.4A CN201910518947A CN110153442B CN 110153442 B CN110153442 B CN 110153442B CN 201910518947 A CN201910518947 A CN 201910518947A CN 110153442 B CN110153442 B CN 110153442B
- Authority
- CN
- China
- Prior art keywords
- solution
- silver
- gold
- nano
- silver alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention relates to a nanometer gold and silver alloy solution with affinity to fiber and a preparation method thereof, the preparation method comprises the steps of firstly respectively adding silver ions and gold ions into deionized water solution of amino-terminated hyperbranched polymer, stirring and heating to respectively prepare a nanometer silver solution and a nanometer gold solution, then mixing the nanometer silver solution and the nanometer gold solution according to a proportion, carrying out high-temperature hydrothermal reaction, and then cooling to prepare a nanometer gold and silver alloy solution with a core-shell structure; the nano gold-silver alloy is in a quasi-spherical shape, and the particle size is 2-30 nm; the nano gold-silver alloy solution can be completely adsorbed to the surface of the fiber at high temperature, silver ions are not released in the using process, and the nano gold-silver alloy solution has good biological safety; the composite material has strong molecular recognition and binding capacity on fibers such as cotton, silk, wool, calcium alginate fibers, chitin and the like, and can be completely assembled on the surface of the fibers in a normal-temperature or high-temperature water bath, so that the problems of poor affinity between the nano material and the fibers, low loading efficiency and environmental pollution are solved.
Description
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a nano gold-silver alloy solution with affinity to fibers and a preparation method thereof.
Background
With the continuous development of nano technology, the synthesis and development of nano noble metals are also continuously advanced. The nano metal material has a series of excellent physical and chemical properties and is vital to modern industry. For example, precious metals such as nanogold, silver, platinum and the like have extremely strong surface Raman enhancement effect, can be widely applied to trace element detection, replaces the traditional ICP detection, reduces the cost and can realize online rapid detection. The nano noble metal also has excellent catalytic effect and is the most important reagent in chemistry and chemical engineering. The nanometer platinum is the best of noble metal catalysts, the nanometer platinum can catalyze hydrogen oxidation reaction at normal temperature, and the platinum-based hydrogen fuel cell is one of the technological breakthroughs of new energy automobiles. Secondly, noble metals such as nano-silver can catalyze CO2 to be CO, and the method has great significance for energy regeneration. And thirdly, the nano metal has certain catalytic performance, can effectively degrade organic molecules and has certain potential in the aspect of sewage treatment. Finally, the nano noble metal has excellent antibacterial effect. Wherein the nano silver has the most excellent antibacterial effect.
Compared with nano platinum, the nano gold and the nano silver have excellent performances, high reserves and low price. Therefore, in recent years, the research on nano gold and silver is gradually a research hotspot. Related researches mainly focus on further improving the performances of catalysis, surface plasma excitation, antibiosis and the like. Compared with single metal, the nano alloy can inherit the performance among different components, and meanwhile, the catalytic performance and the like of the nano alloy can be greatly improved through crystal interface design. Researches show that the nano gold-silver alloy has the advantages that the single component does not have in the antibacterial field, and researchers indicate that the antibacterial performance of the nano alloy is superior to that of the nano silver under the same concentration, the oxidation resistance is obviously improved, and the nano alloy has higher safety.
Nevertheless, the application of nano gold-silver alloy in the antibacterial field also has many problems which are difficult to overcome. Firstly, the stability of the high-concentration nano gold-silver alloy solution is not good; the agglomeration, oxidation and the like of the nano alloy can directly influence the antibacterial effect and the antibacterial durability of the alloy, the shelf life of the product is reduced, and the product is unfavorable for industrial production. Secondly, the nano alloy lacks necessary active groups, is difficult to be firmly combined to the surface of organic fibers, and has the problems of low dye-uptake rate, high content of nano wastewater and the like in the dyeing process; this not only reduces the efficiency of functional finishing, increases the cost, but also causes precious metal waste and related environmental pollution problems. Third, the safety of the nano-alloy is a problem.
For example, chinese patent CN101225227B discloses a hyperbranched polyamidoamine and metal nano-composite in the field of nanotechnology, and a preparation method and an application thereof, wherein the composite is composed of a polymer and metal nanoparticles, the polymer is hyperbranched polyamidoamine obtained by performing end-capping modification on vinyl-terminated hyperbranched polyamidoamine with different amine-containing organic small molecules, and the content of the hyperbranched polyamidoamine is 89 wt% -98 wt%, and the metal nanoparticles are gold or silver nanoparticles, and the content of the metal nanoparticles is 2 wt% -11 wt%. Chinese patent application CN108277637A discloses a method for preparing a functional textile doped with N-Au titanium dioxide nanowires, which comprises the steps of adding a mixed solution of tetrabutyl titanate and ethanol into a slightly acidic aqueous solution, hydrolyzing the mixed solution to form sol and aging the sol into gel, changing the distribution of hydroxyl groups on the surface of titanium dioxide by using an alkaline condition provided by NaOH, and complexing and reducing metal ions by using an amino-terminated hyperbranched polymer to ensure that the amino-terminated hyperbranched polymer grows directionally on a fabric to obtain the functional textile doped with the N-Au titanium dioxide nanowires. Although the above patent achieves the antibacterial effect, the antibacterial effect is limited, and the adsorptivity to biological fibers such as cotton, hemp, silk, wool is limited, and there is a problem of environmental pollution.
Therefore, how to provide a nano gold-silver alloy solution with affinity to fibers and a preparation method thereof to achieve high stability, high affinity and high adsorptivity to fibers, avoid environmental pollution and high safety is a technical problem to be solved urgently by technical personnel in the field at present.
Disclosure of Invention
In view of this, an object of the present application is to provide a nano gold-silver alloy solution having affinity for fibers and a preparation method thereof, so as to achieve high stability, high affinity and high adsorptivity for fibers, avoid environmental pollution, and have high safety.
In order to achieve the above object, the present application provides the following technical solutions.
A method for preparing a nano gold-silver alloy solution with affinity to fibers comprises the following steps:
s1, adding the silver ion solution into the deionized water solution of the hyperbranched polymer, and heating for a certain time under the condition of stirring to prepare a nano silver solution;
s2, adding the gold ion solution into the deionized water solution of the hyperbranched polymer, and heating for a certain time under the condition of stirring to prepare a nano gold solution;
s3, mixing the nano silver solution prepared in the step S1 and the nano gold solution prepared in the step S2 according to a certain volume ratio, carrying out high-temperature hydrothermal reaction for a certain time, and then naturally cooling to prepare the nano gold-silver alloy solution with the core-shell structure.
Preferably, the silver ion solution in the step S1 is a silver nitrate solution, and the mass ratio of the silver ions to the hyperbranched polymer in the silver nitrate solution is 1: 1-1: 10; the concentration of silver element in the silver nitrate in the deionized water solution is 1-6000 mg/L.
Preferably, the gold ion solution in step S2 is one of a chloroauric acid solution and a bromoauric acid solution, the mass ratio of gold ions to the hyperbranched polymer in the gold ion solution is 1:1 to 1:12, and the concentration of gold element in the deionized water solution is 1 to 5000 mg/L.
Preferably, the hyperbranched polymer in the steps S1 and S2 is one of amino-terminated hyperbranched polyamide, carboxyl-terminated hyperbranched polyamide and hydroxyl-terminated hyperbranched polyamide, and the hyperbranched polymer adopted in the two steps is the same type of hyperbranched polymer with the average molecular weight of 7000-10000.
Preferably, the heating temperature in the step S1 and the step S2 is 60-120 ℃, and the heating time is 0.5-6 h.
Preferably, the volume ratio of the silver element to the gold element in the nano silver solution and the nano gold solution in the step S3 is 1: 10-10: 1, the hydrothermal reaction temperature is 100-130 ℃, and the hydrothermal reaction time is 0.5-5 h.
The nano gold-silver alloy solution with affinity to fibers prepared by the preparation method is quasi-spherical, and the particle size is 2-30 nm; the nano gold-silver alloy has an obvious core-shell structure, gold elements are arranged inside the core shell, and silver elements are arranged outside the core shell.
Preferably, the Zeta potential of the surface of the nano gold-silver alloy is controlled to be +18 to +58 mV; the nano gold-silver alloy solution has stability at the temperature of 20-120 ℃ and the pH value of 3-12.
The method for preparing the functionalized fiber by adopting the nano gold-silver alloy solution comprises the steps of soaking the fiber in the nano gold-silver alloy solution, controlling the bath ratio at 1: 20-1: 200, adsorbing at the temperature of 25-100 ℃ for 0.5-6 h to obtain the functionalized fiber loaded with the nano gold-silver alloy, and controlling the loading capacity of the fiber nano gold-silver alloy at 1-80 mg/g.
Preferably, the fibers are selected from one of cotton, hemp, wool, silk, chitin fibers, calcium alginate fibers and polylactic acid fibers, wherein the loading amount of the calcium alginate fibers is 1-80 mg/g, and the adsorption temperature is normal temperature; the loading range of the silk and wool is 1-20 mg/g, and the adsorption temperature range is 30-100 ℃; the loading range of the chitin fiber is 1-5 mg/g, and the adsorption temperature range is 30-100 ℃; the loading range of cotton and fibrilia is 1-4 mg/g, and the adsorption temperature range is 30-100 ℃; the prepared nano platinum solution can be completely adsorbed to the fibers, the platinum residue of the solution is less than 0.5mg/L, and clean production of nano platinum functional fibers can be realized.
The beneficial technical effects obtained by the invention are as follows:
1) the invention solves the defects in the prior art, and the invention uses the amino-terminated hyperbranched polymer as a protective agent to prepare the nano gold-silver alloy solution with high safety, high affinity to fiber and high solution stability through hydrothermal in-situ; the nano gold-silver alloy solution has extremely high solution stability, oxidation resistance, reproducibility, high temperature resistance and acid and alkali resistance; finally, the nano gold-silver alloy solution has super strong binding capacity to natural fibers;
2) the nano gold and silver can be obtained by mixing and heating the nano silver and the nano gold, the preparation process is continuous, and the problem of batch production of nano gold and silver alloy solution is solved;
3) the nano gold-silver alloy solution has high solution stability, a large number of amino groups and positive charges are arranged on the surface of the nano gold-silver alloy solution, bacteria and viruses can be effectively adsorbed, and the nano gold-silver alloy solution has active antibacterial capability, and antibacterial experiments show that the antibacterial capability of the nano gold-silver alloy solution is stronger than that of the nano silver solution; the nano gold-silver alloy solution has high-temperature self-repairability, and can reduce the oxidized metal simple substance into a simple substance again under the action of high temperature; the nano gold-silver alloy solution has high temperature stability;
4) the nano gold-silver alloy solution has strong adsorption binding capacity on biological fibers such as cotton, hemp, silk, wool and the like, and can be adsorbed to the surface of the fibers by 100 percent at normal temperature or in a heating state, so that the problems of low dyeing efficiency of the nano alloy, poor compatibility with the biological fibers and environmental pollution are thoroughly solved; and the nano gold-silver alloy solution does not release silver ions, so that the biological safety is high.
The foregoing description is only an overview of the technical solutions of the present application, so that the technical means of the present application can be more clearly understood and the present application can be implemented according to the content of the description, and in order to make the above and other objects, features and advantages of the present application more clearly understood, the following detailed description is made with reference to the preferred embodiments of the present application and the accompanying drawings.
The above and other objects, advantages and features of the present application will become more apparent to those skilled in the art from the following detailed description of specific embodiments thereof, taken in conjunction with the accompanying drawings.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts. Throughout the drawings, like elements or portions are generally identified by like reference numerals. In the drawings, elements or portions are not necessarily drawn to scale.
FIG. 1 is Zeta potential diagram of a nanometer gold-silver alloy according to an embodiment of the present invention;
fig. 2 is a fourier infrared spectrum of a nano gold-silver alloy shown in an embodiment of the present invention ((i) is amino-terminated hyperbranched polyamide, (ii) is the nano gold-silver alloy);
FIG. 3 is a TEM image of a nano gold-silver alloy disclosed in the embodiment of the present invention;
FIG. 4 is a cotton fabric loaded with nano gold-silver alloy according to an embodiment of the present invention;
fig. 5 is an SEM image of a nano gold-silver alloy cotton fabric shown in the embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. In the following description, specific details such as specific configurations and components are provided only to help the embodiments of the present application be fully understood. Accordingly, it will be apparent to those skilled in the art that various changes and modifications may be made to the embodiments described herein without departing from the scope and spirit of the present application. In addition, descriptions of well-known functions and constructions are omitted in the embodiments for the sake of clarity and conciseness.
The term "and/or" herein is merely an association describing an associated object, meaning that three relationships may exist, e.g., a and/or B, may mean: the three cases of A alone, B alone and A and B together exist, and the term "/and" in this document describes another associated object relationship, which means that two relationships may exist, for example, A/and B, which may mean: a alone, and both a and B alone, and further, the character "/" in this document generally means that the former and latter associated objects are in an "or" relationship.
It is further noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion.
Example 1
A preparation method of a nano gold-silver alloy solution with affinity to fibers comprises the following steps:
s1, adding the silver ion solution into the deionized water solution of the hyperbranched polymer, and heating for a certain time under the condition of stirring, wherein the heating temperature is 60 ℃, and the heating time is 6 hours, so as to prepare the nano silver solution.
The silver ion solution is a silver nitrate solution, and the mass ratio of silver ions to the hyperbranched polymer in the silver nitrate solution is 1: 1; the concentration of silver element in the silver nitrate in the deionized water solution is 500 mg/L.
The hyperbranched polymer is amino-terminated hyperbranched polyamide with the average molecular weight of 7000.
S2, adding the gold ion solution into the deionized water solution of the hyperbranched polymer, and heating for a certain time under the stirring condition, wherein the heating temperature is 60 ℃, and the heating time is 6 hours, so as to prepare the nano-gold solution.
The gold ion solution is chloroauric acid solution, the mass ratio of gold ions to the hyperbranched polymer in the gold ion solution is 1:1, and the concentration of gold element in the deionized water solution is 500 mg/L.
The hyperbranched polymer is amino-terminated hyperbranched polyamide with the average molecular weight of 7000.
S3, mixing the nano silver solution prepared in the step S1 and the nano gold solution prepared in the step S2 according to a certain volume ratio, carrying out high-temperature hydrothermal reaction for a certain time, wherein the hydrothermal reaction temperature is 100 ℃, the hydrothermal reaction time is 0.5-5 h, and then naturally cooling to prepare the nano gold-silver alloy solution with the core-shell structure.
Wherein the volume ratio of the silver element to the gold element in the nano silver solution to the nano gold solution is 1: 10.
The nano gold-silver alloy solution with affinity to the fibers prepared by the preparation method has strong adsorption capacity and high temperature stability, and the highest tolerance temperature can reach 140 ℃. As shown in attached figure 1, the Zeta potential diagram of the nano gold-silver alloy solution of the embodiment; the Zeta potential is an important index for representing the stability of a colloidal dispersion system, and the Zeta potential on the surface of the prepared nano gold-silver alloy is +31.38mV (the pH value of the solution is 7.5) according to the figure, which shows that the prepared nano gold-silver alloy solution has higher solution stability and positive surface potential.
As shown in fig. 2, a fourier infrared spectrum of the nano gold-silver alloy solution of the present embodiment; as can be seen from the figure, the hyperbranched polyamide amido B and the amide II groups on the surface of the nano alloy are weakened, which shows that the amide groups form coordination bonds with the metal on the surface of the nano alloy.
As shown in fig. 3, a TEM image of the nano gold-silver alloy of the present example; the graph shows that the nano gold-silver alloy is in a quasi-spherical shape, the particle size is 2-30 nm, the nano gold-silver alloy has an obvious core-shell structure, the color of the core structure is darker, and the shell is lighter, so that gold with a larger atomic number in the nano gold-silver alloy is arranged in the inner part, and silver with a smaller atomic number is arranged on the outer layer.
Soaking the cotton fiber in a nano gold-silver alloy solution, controlling the bath ratio at 1:20, adsorbing for 6h at the temperature of 30 ℃, wherein the nano gold-silver alloy solution becomes a colorless transparent solution, which indicates that the nano alloy is completely adsorbed on the surface of the cotton fiber, so as to obtain the nano gold-silver alloy loaded functionalized fiber, and the loading amount of the fiber nano gold-silver alloy is controlled at 1 mg/g.
As shown in fig. 4, the fabric of the cotton fabric loaded with the nano gold-silver alloy of the present embodiment is bright yellow after finishing, except that the folded portion of the fabric is darker in color, and the other portions are uniform in color, which indicates that the adsorption of the nano gold-silver alloy is more uniform.
As shown in attached figure 5, an SEM image of the prepared nano gold-silver alloy cotton fabric shows that a large number of nano-scale particles are uniformly distributed on the surface of cotton fibers, and the dispersibility of the nano gold-silver alloy on the surfaces of the fibers is better.
Example 2
A preparation method of a nano gold-silver alloy solution with affinity to fibers comprises the following steps:
and S1, adding the silver ion solution into the deionized water solution of the hyperbranched polymer, and heating for a certain time under the stirring condition, wherein the heating temperature is 90 ℃, and the heating time is 3 hours, so as to prepare the nano silver solution.
The silver ion solution is a silver nitrate solution, and the mass ratio of silver ions to the hyperbranched polymer in the silver nitrate solution is 1: 5; the concentration of silver element in the silver nitrate in the deionized water solution is 3000 mg/L.
The hyperbranched polymer is carboxyl-terminated hyperbranched polyamide with the average molecular weight of 8500.
S2, adding the gold ion solution into the deionized water solution of the hyperbranched polymer, and heating for a certain time under the condition of stirring, wherein the heating temperature is 90 ℃, and the heating time is 3 hours, so as to prepare the nano gold solution.
The gold ion solution is a bronzing acid solution, the mass ratio of gold ions to the hyperbranched polymer in the gold ion solution is 1:6, and the concentration of gold element in the deionized water solution is 3000 mg/L.
The hyperbranched polymer is carboxyl-terminated hyperbranched polyamide with the average molecular weight of 8500.
S3, mixing the nano silver solution prepared in the step S1 and the nano gold solution prepared in the step S2 according to a certain volume ratio, carrying out high-temperature hydrothermal reaction for a certain time, wherein the hydrothermal reaction temperature is 120 ℃, the hydrothermal reaction time is 3 hours, and then naturally cooling to prepare the nano gold-silver alloy solution with the core-shell structure.
Wherein the volume ratio of the silver element to the gold element in the nano silver solution to the nano gold solution is 4: 1.
The nano gold-silver alloy solution with affinity to fibers prepared by the preparation method is quasi-spherical, and the particle size is 2-30 nm; the nano gold-silver alloy has an obvious core-shell structure, wherein gold element is arranged inside the core shell, and silver element is arranged outside the core shell.
The surface of the nano gold-silver alloy is provided with a large number of amino groups and positive charges, and the Zeta potential of the surface of the nano gold-silver alloy can be controlled to be +18 to +58 mV; the nano gold-silver alloy solution has stability at the temperature of 20-120 ℃ and the pH value of 3-12.
The silk fiber is soaked in the nano gold-silver alloy solution, the bath ratio is controlled to be 1:100, the adsorption is carried out for 3 hours at the temperature of 60 ℃, at the moment, the nano gold-silver alloy solution becomes colorless transparent solution, the nano alloy is completely adsorbed to the surface of the cotton fiber, the functionalized fiber loaded with the nano gold-silver alloy is obtained, and the loading capacity of the fiber nano gold-silver alloy is controlled to be 2 mg/g.
Example 3
A preparation method of a nano gold-silver alloy solution with affinity to fibers comprises the following steps:
s1, adding the silver ion solution into the deionized water solution of the hyperbranched polymer, and heating for a certain time under the stirring condition, wherein the heating temperature is 120 ℃, and the heating time is 0.5h, so as to prepare the nano silver solution.
The silver ion solution is a silver nitrate solution, and the mass ratio of silver ions to the hyperbranched polymer in the silver nitrate solution is 1: 10; the concentration of silver element in the silver nitrate in the deionized water solution is 6000 mg/L.
The hyperbranched polymer is hydroxyl-terminated hyperbranched polyamide with the average molecular weight of 10000.
S2, adding the gold ion solution into the deionized water solution of the hyperbranched polymer, and heating for a certain time under the condition of stirring, wherein the heating temperature is 120 ℃, and the heating time is 0.5h, so as to prepare the nano gold solution.
The gold ion solution is a bronzing acid solution, the mass ratio of gold ions to the hyperbranched polymer in the gold ion solution is 1:12, and the concentration of gold element in the deionized water solution is 5000 mg/L.
The hyperbranched polymer is hydroxyl-terminated hyperbranched polyamide with the average molecular weight of 10000.
S3, mixing the nano silver solution prepared in the step S1 and the nano gold solution prepared in the step S2 according to a certain volume ratio, carrying out high-temperature hydrothermal reaction for a certain time, wherein the hydrothermal reaction temperature is 130 ℃, the hydrothermal reaction time is 0.5h, and then naturally cooling to prepare the nano gold-silver alloy solution with the core-shell structure.
Wherein the volume ratio of the silver element to the gold element in the nano silver solution to the nano gold solution is 10: 1.
The nano gold-silver alloy solution with affinity to fibers prepared by the preparation method is quasi-spherical, and the particle size is 2-30 nm; the nano gold-silver alloy has an obvious core-shell structure, gold elements are arranged inside the core shell, and silver elements are arranged outside the core shell.
The surface of the nano gold-silver alloy is provided with a large number of amino groups and positive charges, and the Zeta potential of the surface of the nano gold-silver alloy can be controlled to be +18 to +58 mV; the nano gold-silver alloy solution has stability at the temperature of 20-120 ℃ and the pH value of 3-12.
The fibrilia is dipped in the nano gold-silver alloy solution, the bath ratio is controlled to be 1:200, the solution is absorbed for 0.5h at the temperature of 100 ℃, at the moment, the nano gold-silver alloy solution becomes colorless transparent solution, which indicates that the nano alloy is completely absorbed on the surface of the cotton fiber, so that the functionalized fiber loaded by the nano gold-silver alloy is obtained, and the load amount of the fiber nano gold-silver alloy is controlled to be 4 mg/g.
The fiber in the embodiment is suitable for one of cotton, wool, silk, hemp, calcium alginate fiber, chitin fiber and polylactic acid fiber; soaking the fiber in a nano gold-silver alloy solution, controlling the bath ratio at 1: 20-1: 200, adsorbing at the temperature of 30-100 ℃ for 0.5-6 h to obtain the functional fiber loaded with the nano gold-silver alloy, wherein the loading capacity of the nano gold-silver alloy of the fiber is controlled at 1-80 mg/g; the adsorption capacity of the fiber to the nano platinum is as follows: calcium alginate fiber, silk, chitin fiber, cotton fiber and polylactic acid fiber; wherein the loading capacity of the calcium alginate fibers is 1-80 mg/g, and the adsorption temperature is normal temperature; the loading range of the silk and wool is 1-20 mg/g, and the adsorption temperature range is 30-100 ℃; the loading range of the chitin fiber is 1-5 mg/g, and the adsorption temperature range is 30-100 ℃; the loading range of cotton and fibrilia is 1-4 mg/g, and the adsorption temperature range is 30-100 ℃; the prepared nano platinum solution can be completely adsorbed to the fibers, the platinum residue of the solution is less than 0.5mg/L, and clean production of nano platinum functional fibers can be realized.
The nano gold-silver alloy solution prepared by the embodiment can be completely adsorbed to the surface of the fiber at high temperature, silver ions are not released in the using process, and the nano gold-silver alloy solution has good biological safety; the nano-fiber has strong molecular recognition and binding capacity on fibers such as cotton, silk, wool, calcium alginate fiber, chitin and the like, and can be completely assembled on the surface of the fiber in a normal-temperature or high-temperature water bath, so that the problems of poor affinity of the nano-material and the fiber, low loading efficiency and environmental pollution are solved.
The above description is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the present invention, and various modifications and changes may be made by those skilled in the art. Variations, modifications, substitutions, integrations and parameter changes of the embodiments may be made without departing from the principle and spirit of the invention, which may be within the spirit and principle of the invention, by conventional substitution or may realize the same function.
Claims (5)
1. The preparation method of the nano gold-silver alloy solution with affinity to fibers is characterized by comprising the following steps of:
s1, adding the silver ion solution into the deionized water solution of the hyperbranched polymer, and heating for a certain time under the condition of stirring to prepare a nano silver solution;
s2, adding the gold ion solution into the deionized water solution of the hyperbranched polymer, and heating for a certain time under the condition of stirring to prepare a nano gold solution;
the hyperbranched polymer in the steps S1 and S2 is one of amino-terminated hyperbranched polyamide, carboxyl-terminated hyperbranched polyamide and hydroxyl-terminated hyperbranched polyamide, the hyperbranched polymer adopted in the two steps is the same hyperbranched polymer, and the average molecular weight is 7000-10000; the heating temperature in the step S1 and the step S2 is 60-120 ℃, and the heating time is 0.5-6 h;
s3, mixing the nano silver solution prepared in the step S1 and the nano gold solution prepared in the step S2 according to the volume ratio of the silver element to the gold element in the nano silver solution to the nano gold solution being 1: 10-10: 1, carrying out high-temperature hydrothermal reaction at the temperature of 100-130 ℃ for 0.5-5 h, and then carrying out natural cooling to prepare a nano gold-silver alloy solution with a core-shell structure;
the nano gold-silver alloy in the nano gold-silver alloy solution is in a quasi-spherical shape, the particle size is 2-30 nm, the nano gold-silver alloy solution has an obvious core-shell structure, gold is arranged inside the core shell, and silver is arranged outside the core shell.
2. The nano gold-silver alloy solution with affinity for fibers according to claim 1, wherein the silver ion solution in step S1 is a silver nitrate solution, and the mass ratio of silver ions to the hyperbranched polymer in the silver nitrate solution is 1: 1-1: 10; the concentration of silver element in the silver nitrate in the deionized water solution is 1-6000 mg/L.
3. The nano gold-silver alloy solution with affinity for fibers according to claim 1, wherein the gold ion solution in step S2 is one of chloroauric acid solution and bromoauric acid solution, the mass ratio of gold ions to hyperbranched polymer in the gold ion solution is 1: 1-1: 12, and the concentration of gold element in deionized water solution is 1-5000 mg/L.
4. The nano gold-silver alloy solution as claimed in claim 1, wherein the surface Zeta potential of the nano gold-silver alloy is controlled to be +18 to +58 mV; the nano gold-silver alloy solution has stability at the temperature of 20-120 ℃ and the pH value of 3-12.
5. The method for preparing the functionalized fiber by adopting the nano gold-silver alloy solution as set forth in any one of claims 1 to 4 is characterized in that: soaking the fiber in a nano gold-silver alloy solution, controlling the bath ratio at 1: 20-1: 200, and adsorbing at the temperature of 25-100 ℃ for 0.5-6 h to obtain the functional fiber loaded with the nano gold-silver alloy, wherein the loading capacity of the nano gold-silver alloy of the fiber is controlled at 1-80 mg/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910518947.4A CN110153442B (en) | 2019-06-16 | 2019-06-16 | Nano gold-silver alloy solution with affinity to fibers and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910518947.4A CN110153442B (en) | 2019-06-16 | 2019-06-16 | Nano gold-silver alloy solution with affinity to fibers and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110153442A CN110153442A (en) | 2019-08-23 |
| CN110153442B true CN110153442B (en) | 2022-06-17 |
Family
ID=67625114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910518947.4A Active CN110153442B (en) | 2019-06-16 | 2019-06-16 | Nano gold-silver alloy solution with affinity to fibers and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110153442B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111395005A (en) * | 2020-05-15 | 2020-07-10 | 嘉兴市菲尔欣制衣股份有限公司 | Production process of mothproof and bacteriostatic woolen sweater |
| CN112480581B (en) * | 2020-11-30 | 2022-03-18 | 苏州大学 | Preparation method of modified polyvinyl alcohol/nano metal composite flexible tensile strain sensing material |
| CN114346252B (en) * | 2021-12-30 | 2023-12-01 | 南通大学 | Nano silver colloid solution, preparation method thereof and washing-resistant antibacterial antiviral fabric |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9446953B2 (en) * | 2007-07-12 | 2016-09-20 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Fabrication of metallic hollow nanoparticles |
| CN101225227B (en) * | 2008-01-31 | 2010-09-08 | 上海交通大学 | Over-branched polyamidoamine and metal nano compound as well as preparation method and uses thereof |
| CN101307563B (en) * | 2008-06-17 | 2010-09-15 | 苏州大学 | Nanometer silver antibiotic textile finishing method |
| CN101318224B (en) * | 2008-06-17 | 2010-08-25 | 苏州大学 | Method of preparing nano-silver water solution |
| CN101758244B (en) * | 2010-01-29 | 2011-08-31 | 浙江大学 | Preparation method for water-soluble precious metal nano particle |
| CN101786170B (en) * | 2010-03-26 | 2011-09-14 | 上海师范大学 | Method for preparing cauliflower nano gold-silver alloy with surface-enhanced Raman scattering activity |
| JP6207403B2 (en) * | 2012-02-14 | 2017-10-04 | 国立大学法人群馬大学 | Metal fine particle aggregate and method for producing the same |
| CN102941352A (en) * | 2012-11-27 | 2013-02-27 | 上海师范大学 | Preparation method for gold nano particles |
| CN105461935B (en) * | 2015-12-16 | 2019-05-31 | 浙江大学 | The method of dissaving polymer, preparation method and its stable nano silver containing imidazoles |
| CN105709262A (en) * | 2016-03-16 | 2016-06-29 | 张家港耐尔纳米科技有限公司 | Silver-loaded antibacterial dressing and preparation method thereof |
| CN107138737A (en) * | 2017-05-02 | 2017-09-08 | 重庆大学 | The preparation method of electrum rice structure with regulatable plasma resonance absorption characteristic |
| CN107175340B (en) * | 2017-06-09 | 2019-01-29 | 齐鲁工业大学 | A kind of preparation method of core-shell structure Cu@Ag nanoparticle |
| CN107537543B (en) * | 2017-09-11 | 2020-04-21 | 南通纺织丝绸产业技术研究院 | Preparation method of N-Au-Ag co-doped nano titanium dioxide photocatalyst |
| CN109406507B (en) * | 2018-12-10 | 2021-09-24 | 鲁东大学 | Method for detecting silver ions in seawater by adopting stabilized gold nanoparticles |
-
2019
- 2019-06-16 CN CN201910518947.4A patent/CN110153442B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110153442A (en) | 2019-08-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110153442B (en) | Nano gold-silver alloy solution with affinity to fibers and preparation method thereof | |
| Gopinath et al. | Strategies to design modified activated carbon fibers for the decontamination of water and air | |
| Jin et al. | Smart paper transformer: new insight for enhanced catalytic efficiency and reusability of noble metal nanocatalysts | |
| CN107684907B (en) | Noble metal catalyst for catalyzing wet oxidation of industrial wastewater, preparation method and application thereof | |
| Cheng et al. | In situ prepared nanosized Pt-Ag/PDA/PVA-co-PE nanofibrous membrane for highly-efficient catalytic reduction of p-nitrophenol | |
| Esquivel-Peña et al. | Metal nanoparticle–carbon nanotubes hybrid catalysts immobilized in a polymeric membrane for the reduction of 4-nitrophenol | |
| CN108479799A (en) | A kind of original position support type foam cells noble metal catalyst and preparation method thereof | |
| EP1857180A1 (en) | Article comprising fine noble metal particles carried thereon and method for preparation thereof | |
| Hamaloğlu et al. | Magnetic-porous microspheres with synergistic catalytic activity of small-sized gold nanoparticles and titania matrix | |
| CN108314214B (en) | Process for degrading printing and dyeing wastewater through heterogeneous ozone catalysis | |
| CN110697687A (en) | A1 with core-shell structure2O3Preparation method of coated CNTs powder | |
| KR101890463B1 (en) | Method for fabricating hollow metal nano particles and hollow metal nano particles fabricated by the method | |
| CN112186199B (en) | Catalyst for solid polymer fuel cell and preparation method thereof | |
| CN101890368A (en) | Method for preparing carbon-supported high-activity gold or gold-platinum alloy or gold-core platinum-shell structural nano catalyst | |
| Zhang et al. | Green synthesis of lignin-directed palladium nanoparticles/UiO-66-NH2 paper-based composite catalyst for synergistic adsorption-catalysis removal of hexavalent chromium | |
| Han et al. | Robust preparation of catalytic PEI@ FeOOH fiber membrane for efficient dye degradation | |
| CN112221504A (en) | Preparation method of caprolactam hydrofining catalyst, catalyst and method for refining caprolactam by using catalyst | |
| CN105236480B (en) | HCOOBiO nanocrystalline with unique morphology and preparation method thereof | |
| CN101780403B (en) | Method for preparing metal/titanium dioxide composite material | |
| CN111632595B (en) | Preparation method and use method of flexible graphene oxide/AuNRs composite fiber catalyst | |
| JP4773622B2 (en) | Method for producing catalyst for solid polymer electrolyte fuel cell | |
| Kumarage et al. | Application of metal/metal oxide doped electrospun nanofiber membranes in sustainable catalysis | |
| CN112588288B (en) | Preparation method of rhodium-aluminum composite oxide nano hollow powder | |
| CN108203184B (en) | Treatment process for catalytic degradation of printing and dyeing wastewater by ozone | |
| Khalaf et al. | Novel electrocatalysts for ethylene glycol oxidation based on functionalized phosphates of bimetals Mn/Ni: Morphology, crystallinity, and electrocatalytic performance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |